JP2002520383A - Phenylmethoxyiminoacetic acid derivatives as pesticides - Google Patents

Abstract

(57) [Summary] Compound of formula I: Wherein A is a group CH ₂ O or CH ₂ ON ＝ C (R ₁ ); X ₁ and X ₂ are independently C ₁ -C ₄ alkyl; Y is OH, O (C ₁ -C ₄ alkyl), be NH ₂ or NHCH _3; R ₁ is an C ₁ -C ₄ alkyl, cyclopropyl, cyano, trifluoromethyl or C ₁ -C ₄ alkoxy; R is a aryl, heteroaryl or heterocyclyl May be substituted by the same or different substituents] have microbicidal activity and can be used in the agricultural, horticultural and hygiene fields for controlling phytopathogenic fungi.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to novel phenylmethoxyiminoacetic acid derivatives having microbicidal activity, a process for their preparation, pesticidal compositions containing their active ingredients and those for controlling and preventing phytopathogenic bacteria in agriculture and horticulture Regarding the use of

The new compounds have the formula I:

Embedded image

[Wherein A is a group CH_TwoO or CH_TwoON = C (R₁); X₁And X_TwoAre independently of each other C₁~ C_FourY is OH, O (C₁~ C_FourAlkyl), NH_TwoOr NHCH_ThreeR₁Is C₁~ C_FourAlkyl, cyclopropyl, cyano, trifluoromethyl or
C₁~ C_FourR is aryl, heteroaryl or heterocyclyl, wherein said group is halogen
N; C₁~ C₆Alkyl; C₁~ C_FourAlkyl, halogen, C₁~ C_FourAlkoxy, C ₁ ~ C_FourSame or different substituents selected from halogenalkyl or cyano
Aryl more optionally mono- to tri-substituted; C₁~ C₆Alkoxy; halo
Gen-C₁~ C₆Alkoxy; C₁~ C_FourAlkyl, halogen, C₁~ C_FourAlkoxy
, C₁~ C_FourSame or different substitution selected from halogenalkyl or cyano
Aryloxy optionally mono- to tri-substituted by a group; halogen-C₁
~ C₆Alkyl; C₁~ C₆Alkylthio; halogen-C₁~ C₆Alkylthio; C₁ ~ C₆Alkylsulfinyl; halogen-C₁~ C₆Alkylsulfinyl; C₁~
C₆Alkylsulfonyl; halogen-C₁~ C₆Alkylsulfonyl; C_Two~ C₆A
Lucenyl; C_Two~ C₆Alkenyloxy; C_Two~ C₆Alkynyl; C_Three~ C₆Alkini
Roxy; halogen-C_Two~ C₆Alkenyl; halogen-C_Two~ C₆Alkenyloxy
C; Halogen-C_Two~ C₆Alkynyl; halogen-C_Three~ C₆Alkynyloxy; C ₁ ~ C₆Alkylcarbonyl; halogen-C₁~ C₆Alkylcarbonyl; C₁~ C₆ Alkoxycarbonyl; halogen-C₁~ C₆Alkoxycarbonyl; C₁~ C₆A
Alkylaminocarbonyl; di (C₁~ C₆Alkyl) aminocarbonyl
The alkyl groups may be the same or different.₁~ C₆Alkyl)
Nocarbonyl; C₁~ C₆Alkylaminothiocarbonyl; di (C₁~ C₆Alkyl
A) aminothiocarbonyl wherein said alkyl groups are the same or different
Moyoji (C₁~ C₆Alkyl) aminothiocarbonyl; C₁~ C₆Alkylamino
; Di (C₁~ C₆Alkyl) amino; NO_Two; Unsubstituted C₁~ C_FourAlkylenedioxy
Is a group or C₁~ C_FourMonosubstituted by alkyl and / or halogen
~ Tetrasubstituted C₁~ C_FourAlkylenedioxy group; CN; SF_FiveOCN and
And C (= NOR_Two) -ZR_ThreeSame or different one selected from the group consisting of
Or an aryl or heteroaryl that may be substituted with a plurality of substituents
R or heterocyclyl; R_TwoAnd R_ThreeAre independently hydrogen or C₁~ C₆Z is a direct bond, O, S, NH or N (C₁~ C₆Alkyl)).

Formula I is intended to include all possible isomeric forms and mixtures thereof, such as racemic mixtures and optional [E / Z] mixtures.

[0005] Alkyl is straight-chain alkyl, for example methyl, ethyl, propyl, butyl, pentyl or hexyl, or branched alkyl, for example isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl. is there.

Alkenyl is straight-chain alkenyl such as vinyl, 1-methylvinyl, allyl,
1-butenyl or 2-hexenyl, or branched alkenyl, such as isopropenyl.

Alkynyl is straight-chain alkynyl, such as propargyl, 2-butynyl or 5-hexynyl, or branched alkynyl, such as 2-ethynylpropyl or 2-propargylisopropyl. Alkylenedioxy is -O (alkylene) O-.

[0008] Alkylene is straight-chain alkylene, such as -CH ₂ CH _2- , -CH ₂ CH ₂ CH ₂ -or -CH ₂ C
H ₂ CH ₂ CH _2- , or branched alkylene, such as -CH (CH ₃ )-, -CH (C ₂ H ₅ )-, -C (CH ₃ ) _2- ,
—CH (CH ₃ ) CH ₂ — or —CH (CH ₃ ) CH (CH ₃ ) —.

[0009] Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. Halogenalkyl can contain the same or different halogen atoms. Aryl represents phenyl or naphthyl, preferably phenyl.

Heteroaryl has from 5 to 9 ring members in one or two rings, of which one to three members are heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen. Represents a cyclic aromatic group which is an atom. One or two benzene rings may be fused on the heterocycle, and attachment to the rest of the molecule takes place via either the hetero or benzene component. Examples of heteroaryl include benzimidazolyl, benzisoxazolyl, benzoisothiazolyl, benzocoumaryl, benzofuryl, benzothiadiazolyl, benzothiazolyl, benzothienyl, benzoxazolyl, benzooxadiazolyl, quinazolinyl, quinolyl, quinoxalinyl, carbazolyl , Dihydrobenzofuryl, furyl, imidazolyl, indazolyl, indolyl, isoquinolinyl, isothiazolyl, isoxazolyl, methylenedioxyphenyl,
Ethylenedioxyphenyl, naphthyridinyl, oxazolyl, phenanthridinyl, phthalazinyl, pteridinyl, purinyl, pyrazinyl, pyrazolyl, pyridazinyl, pyrazolo [3,4-b] pyridyl, pyridyl, pyrimidinyl, pyrrolyl, tetrazolyl, oxadiazolyl, thiadiazolyl, thiazolyl, Thienyl,
Triazinyl and triazolyl.

[0011] Pyridyl, pyrazinyl, pyrimidinyl, thiazolyl, quinolinyl and thienyl are preferred.

Heterocyclyl represents a 5- to 7-membered non-aromatic ring having 1 to 3 heteroatoms selected from the group consisting of N, O and S. Preference is given to non-aromatic 5- and 6-membered rings having one nitrogen atom as a heteroatom and optionally one more heteroatom. Piperidinyl, morpholinyl, pyrrolidinyl, pyrazolinyl, thiazolinyl and oxazolinyl are preferred.

Among the compounds of formula I, preference is given to (1) a) A is a group CH ₂ O; or b) A is a group CH ₂ ONＯＮC (R ₁ ), wherein R ₁ is CH ₃ C) X ₁ and X ₂ are methyl; or d) Y is OCH ₃ or NHCH ₃ .

Further, in combination with one of the above groups (1) a to (1) d, R has the following meaning
Also preferred are a group of compounds: (2) unsubstituted or halogen, C₁~ C₆Alkyl, C₁~ C₆Halogen al
Kill, C₁~ C₆Alkoxy, C₁~ C₆Haloalkoxy, C_Two~ C₆Alkenyl, C _Two ~ C₆Alkenyloxy, C_Two~ C₆Alkynyl, C_Three~ C₆Alkynyloxy, C ₁ ~ C₆Same or different selected from alkoxycarbonyl, cyano or OCN
Phenyl mono- to tri-substituted by the substituents:

(3) phenyl substituted by C (＝ NOR ₂ ) —Z—R _3, wherein R ₂ and R ₃ independently of one another represent hydrogen or C ₁ -C ₄ alkyl and Z is a direct bond Represents)

(4) Unsubstituted pyridyl, pyrimidyl, furyl, thienyl, oxazolyl, isothio
Xazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl or
Lazolinyl, or halogen, cyano, nitro, aminocarbonyl,
C₁~ C_FourAlkyl, C₁~ C_FourHalogen alkyl, C₁~ C_FourAlkylcarbonyl,
C₁~ C_FourAlkylsulfonyl, C₁~ C₆Alkylsulfoxyl, C_Three~ C₆Cyclo
Alkyl, C₁~ C_FourAlkoxy, C₁~ C_FourHalogen alkoxy, C₁~ C₆Arco
Xycarbonyl, C₁~ C₆Alkylthio, C₁~ C₆Alkylamino, di-C₁~
C₆Alkylamino, C₁~ C₆Alkylaminocarbonyl, di-C₁~ C₆Archi
Ruaminocarbonyl, C_Two~ C₆Alkenyl, C (= NOR_Two) -ZR_ThreeChoose from
The same or different substituents, or aryl and optionally C₁
~ C_FourAlkyl, halogen, C₁~ C_FourAlkoxy, C₁~ C_FourHalogen alkyl
Mono- or tri-substituted by the same or different substituents selected from
Pyridyl, pyridyl,
Midinyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl,
Isothiazolyl, imidazolyl, pyrazolyl or pyrazolinyl, especially unsubstituted or halogen, cyano, nitro, methyl, ethyl, halogeno
Choose from chill, haloethyl, methoxy, ethoxy, halomethoxy, haloethoxy
Or the same or different substituents, or₁~ C_TwoAlkyl, halogen, C ₁ ~ C_TwoAlkoxy, C₁~ C_TwoSame selected from halogen alkyl or cyano
Or phenyl which may be mono- or disubstituted by different substituents
Pyridyl, pyrimidinyl, furyl, mono- or disubstituted by
, Thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl,
Imidazolyl, pyrazolyl, pyrazolinyl.

The compounds of the formula I are: A) compounds of the general formula II:

Embedded image Wherein A, R, X ₁ , X ₂ and Y have the meanings given for formula I; and an oxidizing agent such as a quinone, preferably chloranil or DDQ (2,3-dichloro-5,6-dicyano) -1,4-benzoquinone), prepared by reacting with atmospheric oxygen, manganese dioxide, selenium dioxide, N, N, N ', N'-tetramethylethylenediamine / base, or triphenylmethanol in trifluoroacetic acid. You. Compounds of the general formula II are known (WO 97/47592 and WO 97/49672)
Or can be prepared by the methods described therein.

B) A compound of formula I wherein Y is OH, NH ₂ or NHCH ₃ and A, R, X ₁ and X ₂ have the meaning given for formula I, is a compound of formula Ia:

Embedded image Wherein, Y represents O (C ₁ ~C ₄ alkyl), and A, R, X ₁ and X ₂ means has given for formula I] an acid or base in an aqueous or NH _3,, Alternatively, it is produced by reacting with NH ₂ CH ₃ .

C) Compounds of Formula I where Y is O (C ₁ -C ₄ alkyl) or NHCH ₃ are compounds of Formula III:

Embedded image Wherein U is a leaving group such as chlorine, bromine, iodine, OH, mesyloxy, benzenesulfonyloxy or tosyloxy, preferably chlorine or bromine, and the remaining substituents have the meanings described above. Alcohol of IV or oxime of general formula V:

Embedded image Wherein R and R ₁ have the meaning given for formula I.

D) The compound of formula I is a compound of formula VI:

Embedded image Wherein each substituent has the meaning given for formula I, with a methylating agent such as methyl iodide or dimethyl sulfate.

E) A compound of formula VI comprises: a) a compound of formula VII:

Embedded image Wherein each substituent has the meaning given for formula I, with hydroxylamine, or one of its salts.

F) Compound of formula VIII:

Embedded image Wherein each substituent has the meaning given for formula I with nitrous acid or alkyl nitrite.

G) Compounds of formula I wherein A is a group CH ₂ ON = CR ₁ and the remaining substituents have the meanings given for formula I, are compounds of formula IX:

Embedded image With a compound of formula R ₁ —CO—R, wherein each substituent has the meaning given for formula I. All of the above reactions are known per se.

Processes for the preparation of the compounds of the formula I, as well as novel intermediates of the formulas III, VI, VII, VIII and IX, are likewise objects of the present invention. The intermediate has the corresponding (similar to formula II) 1,
The 4-cyclohexadiene derivative is converted to an oxidizing agent such as quinone, preferably chloranil or DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone), atmospheric oxygen, manganese dioxide, selenium dioxide, N, It can be prepared by reacting with N, N ', N'-tetramethylethylenediamine / base or triphenylmethanol in trifluoroacetic acid.

The corresponding 1,4-cyclohexdiene derivatives are known (WO 97/47592 and W
O 97/49672) or by the methods described therein.

The compounds of the formula I have prophylactic and / or therapeutic value as active ingredients for controlling plant pests and can be used in the agricultural or related fields.
The active ingredients of the formula I according to the invention are notable for their excellent activity even at low concentrations, of good plant tolerance and of environmental acceptability. They have very advantageous properties, especially systemic properties, and can be used for the protection of many crops. With the active ingredients of the formula I, plants or plant parts of various crops (fruits, flowers, leaves, stems, tubers, roots)
Pests that emerge above can be prevented or eradicated, and thereby protect the subsequently growing plant parts, for example, against phytopathogenic microorganisms.

The compounds of the formula I are used as dressings for seeds (fruits, rhizomes, grains) and plant cuttings to protect against fungal infections and against phytopathogens present in the soil. Can also be used.

The compounds of the formula I are effective, for example, against phytopathogenic fungi belonging to the following fungi:
Fungi imperfecti (eg, Botrytis, Pyricularia, Helminthosporium, Fusarium)
rium), Septoria, Cercospora and Alternaria]; Basidiomycetes [eg Rhizoctonia (Rhizoctonia)
onia), Hemileia, Puccinia (rust), Ascomycetes (eg, Venturia, Erysiphe, Podosphaera, Monilinia, Uncinnula) (Uncinula)] and oomycetes (eg, Phytophtho)
ra) (Blight fungus), Pythium (Phythium), Plasmopara
(Tangitic yukata)].

Target crops for plant protection use within the scope of the present invention are, for example, the following plant species: cereals (wheat, barley, rye, oats, rice, corn, sorghum and related species); Forage beet); Nika, stone fruits and small fruit trees (apple, pear, plum, peach, almond, cherry, strawberry, raspberry and blackberry); Legumes (Pink beans, lentils, peas and soybeans)
Oil crops (rapeseed, mustard, poppy, olive, sunflower, palm, castor oil plants, cocoa beans and peanuts); Cucurbitaceae plants (pumpkin, cucumber and melon);
Textile plants (cotton, flax, hemp and jute); citrus fruits (orange, lemon, grapefruit and mandarin); vegetables (spinach, lettuce, asparagus, cabbage, carrot, onion, tomato, potato and paprika); Avocados, cinnamon, camphor); and plants such as tobacco, nuts, coffee, eggplant, sugarcane, tea, pepper, grapes, hops, bananas and natural rubber, and ornamental plants.

A further field of application of the active ingredients according to the invention is the protection of strains and materials, which protects stored goods against spoilage and mold. In this case, the compounds I are used in unmodified form or preferably together with excipients customary in pharmaceutical technology. For this purpose, in a known manner, for example, concentrated emulsions, pastes for coating, solutions for direct spraying or dilution, diluted emulsions, wettable powders, soluble powders, powders, granules and also, for example, capsules in polymeric substances Can be formulated into capsules. As with the type of composition, application methods such as spraying, spraying, dusting, dispersing, coating or pouring are selected according to the intended purpose and prevailing circumstances.

[0031] Suitable carriers and additives may be solid or liquid and are suitable in the preparation arts, for example, natural and regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, bulking agents. Agent, binder or fertilizer. The compounds of the formula I can also be mixed with other active ingredients, such as fertilizers, trace element intermediates or other plant protection formulations, in particular other fungicides. Thus, an unexpected synergistic effect can be brought about.

Particularly preferred mixed components are: azoles such as azaconazole, bitertanol, bromconazole, cyproconazole, diphenoconazole, diconinazole, epoxyconazole, fenbuconazole, fluquinconazole, flusilazole, furtria Fol,
Hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, microbutanil, pefurazoate, penconazole, pyrifenox, prochloraz, propiconazole, tebuconazole, tetraconazole, triadimefon, triazimenol, triflumizole, tritico Nazole;

Pyrimidinyl carbinols, such as ancimidol, fenarimol, nuarimol; 2-aminopyrimidines, such as bupirimate, dimethylimyl, ethylimole; morpholines, such as dodemorph, fenpropidine, fenpropimorph, spiroxamine, tridemorph; anilino Pyrimidines, such as cyprodinil, mepanipyrim, pyrimethanil; pyrroles, such as fenpiclonil, fludioxonil; phenylamides, such as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, offleys, oxadixyl;

Benzimidazoles, such as benomyl, carbendazim, debacarb, fberidazole, thiabendazole; dicarboximides, such as clozolinate, diclozolin, iprodione, microzolin, procymidone, vinclozolin; carboxamides, such as carboxin, fenfluram, flutranil, mepronil; Oxycarboxin, thifluzamide;

Guanidines, such as guazatine, dozine, iminoctadine; Strobilurins, such as azoxystrobin, kresoxime-methyl, SSF
-126 (methominostrobin or phenominostrobin); SSF-129 (α-
Methoxyimino-N-methyl-2-[(2,5-dimethylphenoxy) methyl]
Benzeneacetamide), trifloxystrobin (2- [α-{[(α-methyl-3-trifluoromethylbenzyl) imino] oxy} -o-tolyl] glyoxylic acid methyl ester-O-methyl oxime);

Dithiocarbamates, such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb, ziram; N-halomethylthios, such as captafor, captan, diclofluanid, fluoromido, folpet, trifluanid; Cu compounds, For example, Bordeaux solution, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, man copper, oxine copper;

Nitrophenol derivatives such as dinocap, nitrosal-isopropyl; organophosphorus derivatives such as edifenfos, iprobenfos, isoprothiolane, phosdiphen, pyrazophos, tolclofos-methyl;

Micellar compounds, such as acibenzolar-S-methyl, anilazine, blasticidin-S, quinomethionate, chloroneb, chlorothalonyl, simoxanil, dichloron, diclomedin, dichlorane, dietofencarb, dimethomorph, dithianone, etridiazole, famoxadone, flutin, azirimone, ferimson Flusulfamide, fenhexamide, fosetyl-aluminum, himexazole, kasugamycin, metasulfocarb, pendiclone, phthalide,
Polyoxins, probenazole, propamogalb, pyroquilon, quinoxyfen, quintozen, sulflu, triazoxide, tricyclazole, trifolin, validamycin.

A preferred method of applying pesticidal compositions comprising the active ingredients of the formula I or at least one of these active ingredients is foliar application. The frequency and amount of application depends on the severity of the infestation by the intruder in question. However, the permeation of the active ingredient I from the soil through the roots into the plant by irrigating the local formulation of the plant with the liquid formulation or by spraying the substance in the solid (eg granular form) on the soil (soil spraying). Can also (systemic effect). For rice crops, the granules can be sprayed on the rice paddy. By irrigating the kernels or tubers with a liquid formulation of Compound I,
Alternatively, compound I can be applied to seed grains for seed pretreatment by coating them with a solid preparation.

The pesticidal compositions are prepared in a known manner, for example by intimately mixing and / or grinding the active ingredient with extenders, for example solvents, solid carriers and, if desired, surface-active compounds (surfactants). .

The pesticidal compositions usually comprise from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of an active ingredient of the formula I,
99.9-1% by weight, in particular 99.8-5% by weight of solid or liquid additives, and 0-25% by weight
, In particular from 0.1 to 25% by weight of surfactant.

Preferred application rates are usually from 1 g to 2 kg of active substance (AS) per hectare (ha).
), Preferably from 10 g to 1 kg AS / ha, especially from 20 g to 600 g AS / ha. When used as seed dressings, doses of 10 mg to 1 g of active substance per kg of seed are advantageously used.

The composition may also contain additional additives, such as stabilizers, defoamers, viscosity modifiers, binders or tackifiers, as well as fertilizers or other active ingredients to achieve special effects. Good.

Production Example P-1) {4,5-dimethyl-2- [1- (3-trifluoromethylphenyl) ethylideneaminooxymethyl] phenyl} methoxyiminoacetic acid methyl ester 3.15 g of toluene in 40 ml of toluene 4,5-dimethyl-2- [1- (3-trifluoromethylphenyl) ethylideneaminooxymethyl] cyclohexa-1,4-
A solution of dienyl dimethoxyiminoacetic acid methyl ester (as an E / Z mixture for the ethylidene-aminooxy double bond) was treated with 2.0 g of 2,3-dichloro-5,6
As a result of mixing with -dicyano-1,4-benzoquinone (DDQ), a slight exothermic reaction was observed. After stirring at room temperature for 4 hours, the reaction mixture was filtered through Hyflo and the solvent was distilled off on a rotary evaporator. After purification on silica gel using diethyl ether / hexane (1: 3), 2.6 g of the target compound were obtained as a yellowish oil.

[0045] P-2) 2- {4,5- dimethyl-2- [1- (3-triphenylmethyl a phenyl) ethylidene amino oxymethyl] phenyl} -2-methoxyimino -N- methylation acetamide ethanolic A solution of 2.1 g of the ester obtained with P-1 in 10 ml of methylamine (8.03M) was stirred overnight at room temperature. After distilling off excess methylamine and the solvent, 2.0 g of the target compound (E / Z mixture) was obtained in the form of a pale yellow crystalline powder having a melting temperature range of 129-134 ° C.

P-3) (4,5-Dimethyl-2-o-tolyloxymethylphenyl) methoxyiminoacetic acid methyl ester 1.3 g of (4,5-dimethyl-2-o-tolyloxymethyl ) in 15 ml of toluene A solution of cyclohexa-1,4-dienyl) methoxyiminoacetic acid methyl ester was mixed with 1.1 g of DDQ. After stirring at room temperature for 5 hours, toluene / hexane /
The reaction mixture was purified on silica gel using diisopropyl ether (10: 10: 3). After stirring in hexane, the target compound is obtained in the form of white crystals with a melting point of 82-84 ° C. The compounds described in the table below can be prepared in a similar manner.

Table 1 Table Y represents methoxy and R represents in each case a row of table A. Compound of 1.

Embedded image

Table 2 Table Y represents ethoxy and R corresponds in each case to one row of table A. Compound of 1. Table 3 Y represents NHCH ₃ and R corresponds in each case to a row of table A. 1
Compound.

Table 4 Table ₁ General formula I.1 wherein R ₁ represents methyl and Y represents methoxy and R corresponds in each case to a row of table A. Compound of 2.

Embedded image

Table 5 Table _{1 wherein} R ₁ represents methyl and Y represents ethoxy and R corresponds in each case to one row of table A. Compound of 2. Table 6 Table _{1 wherein} R ₁ represents methyl and Y represents NHCH ₃ and R corresponds in each case to one row of table A. Compound of 2. Table 7 Table ₁ General formula I.1 wherein R ₁ represents ethyl and Y represents methoxy and R corresponds in each case to a row of table A. Compound of 2.

Table 8 Table _{1 wherein} R ₁ represents ethyl and Y represents ethoxy and R corresponds in each case to one row of table A. Compound of 2. Table 9 The general formula I.1 in which R ₁ represents ethyl and Y represents NHCH ₃ and R corresponds in each case to a row of table A. Compound of 2. Table 10 Table ₁ General formula I.1 wherein R ₁ represents cyclopropyl and Y represents methoxy and R corresponds in each case to a row of table A. Compound of 2.

Table 11 Table _{1 wherein} R ₁ represents cyclopropyl and Y represents ethoxy and R corresponds in each case to one row of table A. Compound of 2. Table 12 The general formula I.1 in which R ₁ represents cyclopropyl and Y represents NHCH ₃ and R corresponds in each case to a row of table A. Compound of 2. Table 13 R ₁ represents methoxy and Y represents methoxy and has the general formula R corresponds to one line of Table A in each case I. Compound of 2.

Table 14 R ₁ represents methoxy and Y represents ethoxy and R corresponds in each case to one row of table A. Compound of 2. Table 15 Table R ₁ represents methoxy and Y represents NHCH ₃ and R corresponds in each case to one row of table A. Compound of 2. Table 16 Table ₁ General formula I.1 wherein R ₁ represents cyano and Y represents methoxy and R corresponds in each case to a row of table A. Compound of 2.

Table 17 Table R ₁ represents cyano and Y represents ethoxy and R represents in each case one row of table A. Compound of 2. Table 18 Table R ₁ represents cyano and Y represents NHCH ₃ and R in each case corresponds to one row of table A. Compound of 2. Table 19 Table R ₁ represents trifluoromethyl and Y represents methoxy and R corresponds in each case to one row of table A. Compound of 2.

Table 20 Table R ₁ represents trifluoromethyl and Y represents ethoxy and R in each case corresponds to one row of table A. Compound of 2. Formula Table 21 R ₁ represents trifluoromethyl and Y represents NHCH _3, and R corresponds to one line of Table A in each case I. Compound of 2.

[0056]

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[0057]

[Table 8]

[0058]

[Table 9]

Biological Examples In the following disease states, the compounds listed in the table show good activity. Example B-1: Activity against Black Rust Fungus (Puccinia graminis) on Wheat a) Residual Protective Action Six days after seeding, an aqueous spray mixture (0.02% active substance) prepared from a wettable powder of the active ingredient was dropped with water drops. Spray to run off. Twenty-four hours later, the fungus uredospore suspension is infected. 48-hour incubation period (conditions: 95 ° C and 20% relative humidity)
After 100%), the plants are kept at 22 ° C. in a greenhouse. The fungal contamination is evaluated 12 days after infection.

B) Systemic action 5 days after sowing, an aqueous spray mixture (0.006% active based on soil volume) prepared from a wettable powder of the active ingredient is drenched on the wheat plants. Take care that the spray mixture does not touch the parts of the plant above the ground. After 48 hours, the plants are infected with a euspore suspension of the fungus. After an incubation period of 48 hours (conditions: temperature 20 ° C. and relative humidity 95-100%), the plants are kept at 22 ° C. in a greenhouse. The fungal contamination is evaluated 12 days after infection.

Example B-2: Activity against Phytophthora infestans on tomato a) Residual protective action After cultivation for 3 weeks, an aqueous spray mixture prepared from a wettable powder of the active ingredient was added to tomato plants (
(0.02% active substance) is sprayed on until the water drops run off and, after 24 hours, the fungal sporangial suspension is infected. Five days after infection, fungal contamination is assessed. During that period, the conditions of 90-100% relative humidity and 20 ° C are maintained.

B) Systemic action After cultivation for 3 weeks, an aqueous spray mixture prepared from a wettable powder of the active ingredient (0.006% active ingredient based on soil volume) is irrigated onto tomato plants. Take care that the spray mixture does not touch parts of the plant above the ground. After 48 hours, the plants are infected with a sporangial suspension of the fungus. Five days after infection, fungal contamination is assessed. During that period, the conditions of 90-100% relative humidity and 20 ° C are maintained.

Example B-3: Activity against brown spot disease fungus (Cercospora arachidicola) on peanuts An aqueous spray mixture prepared from a wettable powder of the active ingredient ( 10-15 cm long )
(0.02% active substance) is sprayed on until the water drops run off and after 48 hours the conidia suspension of the fungus is infected. Incubate the plants at 21 ° C in humid for 72 hours,
It is then kept in the greenhouse until typical spots appear. On day 12 after infection, the activity of the active substance is evaluated based on the number and size of the spots.

Example B-4: Activity against downy mildew fungus on the grape (Plasmopara viticola) An aqueous spray mixture (0.02% active) prepared from a wettable powder of the active ingredient on grape cuttings (spikes) at the 4-5 leaf stage Substance) until water drops run off and after 24 hours,
Infect the sporangial suspension of the fungus. Fungal contamination is assessed 6 days after infection. During this period, the conditions of 95-100% relative humidity and 20 ° C are maintained.

Example B-5: Activity against Colletotrichum lagenarium on cucumber After a cultivation period of 2 weeks, cucumber plants are sprayed with an aqueous spray mixture (concentration 0.002%) prepared from a wettable powder of the active ingredient. . Two days later, a spore suspension of the fungus (
1.5 × 10 ⁵ spores / ml) and incubate at 23 ° C. under humid conditions for 36 hours. The incubation is then continued at normal humidity and about 22 ° C. Eight days after infection, fungal contamination is assessed.

Example B-6: Residual protection against scab fungus (Venturia inaequalis) on apples Apple cuttings with shoots of 10 to 20 cm in length are sprayed on a cutting mixture prepared from a wettable powder of the active ingredient (0.02% active substance). ) Is sprayed until water drops run down. Twenty-four hours later, apple plants are infected with a conidiospore suspension of the fungus. The plants are then incubated for 5 days at 90-100% relative humidity and kept in a greenhouse at 20-24 ° C for another 10 days. The fungal contamination is evaluated 12 days after infection.

Example B-7: Activity against barley powdery mildew (Erysiphe graminis) on barley a) Residual protective action A barley plant having a seedling length of about 8 cm was sprayed with a spray mixture (0.02
% Active substance) until the water drops run out and sprinkle with the conidia of the fungus 3-4 hours later. Infected plants are maintained at 22 ° C in a greenhouse. The fungal contamination is evaluated 12 days after infection.

B) Systemic action A barley plant with a seedling length of about 8 cm is treated with an aqueous spray mixture prepared from a wettable powder of the active ingredient (
Irrigation with 0.002% active based on soil volume). Take care that the spray mixture does not touch the plant parts on the ground. 48 hours later, the treated plants are sprinkled with the conidia of the fungus. The infected plants are then maintained at 22 ° C. in a greenhouse. The fungal contamination is evaluated 12 days after infection.

Example B-8: Activity against powdery mildew fungus (Podosphaera leucotricha) on apple branch
A spray mixture (0.06% active substance) is sprayed on apple cuttings with new branches about 15 cm in length. After 24 hours, the treated plants are infected with a conidia suspension of the fungus and 70
Maintain the treated plants in a climatic chamber at 20% relative humidity and 20% relative humidity. The fungal contamination is evaluated 12 days after infection.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR , BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS , JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZA, ZWF terms (reference) 4H006 AA01 AA03 AB03 BW21 4H011 AA01 AA03 BB06 DA15 DD03 DE15

Claims (8)

[Claims] 1. The following formula I:Wherein A is a group CH_TwoO or CH_TwoON = C (R₁); X₁And X_TwoAre independently of each other C₁~ C_FourY is OH, O (C₁~ C_FourAlkyl), NH_TwoOr NHCH_ThreeR₁Is C₁~ C_FourAlkyl, cyclopropyl, cyano, trifluoromethyl or
C₁~ C_FourR is aryl, heteroaryl or heterocyclyl, wherein said group is halogen
N; C₁~ C₆Alkyl; C₁~ C_FourAlkyl, halogen, C₁~ C_FourAlkoxy, C ₁ ~ C_FourSame or different substituents selected from halogenalkyl or cyano
Aryl more optionally mono- to tri-substituted; C₁~ C₆Alkoxy; halo
Gen-C₁~ C₆Alkoxy; C₁~ C_FourAlkyl, halogen, C₁~ C_FourAlkoxy
, C₁~ C_FourSame or different substitution selected from halogenalkyl or cyano
Aryloxy optionally mono- to tri-substituted by a group; halogen-C₁
~ C₆Alkyl; C₁~ C₆Alkylthio; halogen-C₁~ C₆Alkylthio; C₁ ~ C₆Alkylsulfinyl; halogen-C₁~ C₆Alkylsulfinyl; C₁~
C₆Alkylsulfonyl; halogen-C₁~ C₆Alkylsulfonyl; C_Two~ C₆A
Lucenyl; C_Two~ C₆Alkenyloxy; C_Two~ C₆Alkynyl; C_Three~ C₆Alkini
Roxy; halogen-C_Two~ C₆Alkenyl; halogen-C_Two~ C₆Alkenyloxy
C; Halogen-C_Two~ C₆Alkynyl; halogen-C_Three~ C₆Alkynyloxy; C ₁ ~ C₆Alkylcarbonyl; halogen-C₁~ C₆Alkylcarbonyl; C₁~ C₆ Alkoxycarbonyl; halogen-C₁~ C₆Alkoxycarbonyl; C₁~ C₆A
Alkylaminocarbonyl; di (C₁~ C₆Alkyl) aminocarbonyl
The alkyl groups may be the same or different.₁~ C₆Alkyl)
Nocarbonyl; C₁~ C₆Alkylaminothiocarbonyl; di (C₁~ C₆Alkyl
A) aminothiocarbonyl wherein said alkyl groups are the same or different
Moyoji (C₁~ C₆Alkyl) aminothiocarbonyl; C₁~ C₆Alkylamino
; Di (C₁~ C₆Alkyl) amino; NO_Two; Unsubstituted C₁~ C_FourAlkylenedioxy
Is a group or C₁~ C_FourMonosubstituted by alkyl and / or halogen
~ Tetrasubstituted C₁~ C_FourAlkylenedioxy group; CN; SF_FiveOCN and
And C (= NOR_Two) -ZR_ThreeSame or different one selected from the group consisting of
Or an aryl or heteroaryl that may be substituted with a plurality of substituents
R or heterocyclyl; R_TwoAnd R_ThreeAre independently hydrogen or C₁~ C₆Z is a direct bond, O, S, NH or N (C₁~ C₆Alkyl)]. Wherein or halogen R is unsubstituted phenyl, C ₁ -C ₆ alkyl, C ₁ -C ₆ halogenalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₂ ~ C ₆ alkenyl, C ₂ -C ₆ alkenyloxy, C ₂ -C ₆ alkynyl, C ₃ -C ₆ alkynyloxy, C ₁ -C ₆ alkoxycarbonyl, cyano or O
The compound according to claim 1, which is phenyl mono- to tri-substituted by the same or different substituents selected from CN. 3. R is phenyl substituted by C (＝ NOR ₂ ) —Z—R ₃ , wherein R ₂ and R ₃ independently of one another represent hydrogen or C ₁ -C ₄ alkyl and The compound of claim 1, wherein represents a direct bond. 4. R is pyridyl, pyrimidyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl or pyrazolinyl, and each group is unsubstituted or halogen,
Cyano, nitro, aminocarbonyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ alkylcarbonyl, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₆ alkylsulfoxyl, C ₃ ~ C ₆ cycloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ halogenalkoxy, C ₁ -C ₆ alkoxycarbonyl, C ₁ -C ₆ alkylthio,
C ₁ -C ₆ alkylamino, di -C ₁ -C ₆ alkylamino, C ₁ -C ₆ alkylaminocarbonyl, di -C ₁ -C ₆ alkylaminocarbonyl, C ₂ -C ₆ alkenyl,
By the same or different substituents selected from C (＝ NOR ₂ ) —Z—R ₃ , or aryl and C ₁ -C ₄ alkyl, halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄
C ₄ with an aryl which may have been single-to trisubstituted by identical or different substituents selected from halogen alkyl or cyano, which is mono--trisubstituted compound of claim 1. 5. A process for the preparation of a compound of formula I, which comprises: A) a compound of formula II: Wherein A, R, X ₁ , X ₂ and Y have the meaning given for formula I with an oxidizing agent; or B) Y is OH, NH ₂ or NHCH ₃ and A, R, X ₁ and X ₂ are of the formula I
To prepare a compound of formula I having the meaning given for a compound of formula Ia: Wherein, Y represents O (C ₁ ~C ₄ alkyl), and A, R, X ₁ and X ₂ means has given for formula I] an acid or base in an aqueous or NH _3,, Or reacting with NH ₂ CH ₃ ; or C) to prepare a compound of formula I wherein Y is (C ₁ -C ₄ alkyl) or NHCH ₃ , a compound of formula III: Wherein U is a leaving group and the remaining substituents have the meanings described above, with an alcohol of general formula IV or an oxime of general formula V: Wherein R and R ₁ have the meanings given for formula I; or D) a compound of formula VI below: Wherein each substituent has the meaning given for formula I, with a methylating agent; or G) A is a group CH ₂ ON = CR ₁ and the remaining substituents are given for formula I To prepare a compound of formula I having the indicated meaning, a compound of formula IX: With a compound of formula R ₁ —CO—R, wherein each substituent has the meaning given for formula I. 6. The following group: Wherein each substituent has the meaning given for formula I, and U is a leaving group. 7. A pesticidal composition comprising an effective amount of the compound according to claim 1 as an active ingredient together with a suitable carrier. 8. A method for protecting plants against harmful fungi, which comprises applying the compound according to claim 1 to said plants or to their location.